Secondary battery

ABSTRACT

A secondary battery has a battery body and a restraint. The battery body has a plurality of stacked power generation elements. The restraint restrains the battery body. The restraint has a first contact section (for applying a restraining force to an outermost layer surface (e.g., a negative electrode collector) of the battery body. The restraint is configured so that a stress occurring at a boundary of a non-contact region and a contact region of the first contact section is less than a breaking strength of the negative electrode collector, and the stress is based on the restraining force and on expansion and contraction of a negative electrode due to a change in volume of a negative electrode active material layer caused by charging and discharging.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a U.S. national stage application of InternationalApplication No. PCT/JP2017/009062, filed on Mar. 7, 2017.

BACKGROUND Technical Field

The present invention relates to a secondary battery.

Background Information

A secondary battery has a battery body and a restraint. The battery bodyhas a plurality of stacked power generation elements. The powergeneration elements have a positive electrode having a positiveelectrode collector in which a positive electrode active material layeris disposed on a surface thereof, an electrolyte layer for retaining anelectrolyte, and a negative electrode having a negative electrodecollector in which a negative electrode active material layer isdisposed on a surface thereof. The positive electrode active materiallayer and the negative electrode active material layer face each other,interposed by the electrolyte layer.

The restraint is constituted from a pressure-sensitive-adhesive tapeprovided in order to prevent misalignment of constituent materials ofthe battery body (see International Publication No. WO 2014/188607, forexample). The pressure-sensitive-adhesive tape extends from oneoutermost layer of the battery body, the layer being outermost in astacking direction of the power generation elements, to anotheroutermost layer of the battery body via a side of the battery body, andapplies a restraining force to the one outermost layer and the otheroutermost layer of the battery body.

SUMMARY

A negative electrode active material containing silicon has been appliedin a negative electrode active material layer in recent years for thepurpose of increasing battery capacity.

However, silicon characteristically undergoes a large change in volumein response to charging and discharging of the secondary battery, andsignificantly expands and contracts in a direction of a planeintersecting with the stacking direction of the power generationelements. Problems therefore arise in the negative electrode collectorpositioned in at least one outermost layer of the battery body.

For example, in a contact region of the negative electrode collector, inwhich the pressure-sensitive-adhesive tape is in contact with thenegative electrode collector, expansion and contraction is restricted,and there is therefore a marked difference between the contact regionand a non-contact region with regard to an amount of expansion andcontraction. Splitting of the negative electrode collector can thereforeoccur at a boundary (periphery of the contact region) of the contactregion and the non-contact region.

Localized splitting of the negative electrode collector reduces batteryoutput and/or battery capacity, and the localized splitting grows as aresult of repeated charging and discharging of the secondary battery andcan cause cycle characteristics (service life) to deteriorate.

The present invention was contrived in order to overcome the problems ofthe prior art described above, and an object of the present invention isto provide a secondary battery in which it is possible to suppresssplitting of a negative electrode collector caused by contraction andexpansion of a silicon-containing negative electrode active materiallayer.

The present invention for achieving the abovementioned object is asecondary battery comprising a battery body having a plurality ofstacked power generation elements, and a restraint for restraining thebattery body in a stacking direction of the power generation elements, afirst contact section of the restraint for applying a restraining forceto a surface of one outermost layer of the battery body being configuredso that a stress occurring at a boundary of a non-contact region and acontact region of the first contact section is less than a breakingstrength of the negative electrode collector, the stress being based onthe restraining force and expansion and contraction of a negativeelectrode due to a change in volume of a negative electrode activematerial layer caused by charging and discharging.

The present invention is configured so that the stress occurring at theboundary of the non-contact region and the contact region of the firstcontact section is less than the breaking strength of the negativeelectrode collector, and the stress is relieved. Splitting of thenegative electrode collector at the boundary (periphery of the contactregion) of the contact region and the non-contact region is thereforesuppressed. In other words, a secondary battery can be provided in whichit is possible to suppress splitting of the negative electrode collectorcaused by contraction and expansion of the silicon-containing negativeelectrode active material layer.

Other objects, features, and characteristics of the present inventionwill become apparent from the preferred embodiments presented asexamples in the following description and the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an oblique view illustrating a secondary battery according toan embodiment of the present invention;

FIG. 2 is a sectional view of the secondary battery shown in FIG. 1;

FIG. 3 is a sectional view illustrating a battery body and powergeneration elements shown in FIG. 2;

FIG. 4 is a plan view illustrating a negative electrode shown in FIG. 3;

FIG. 5 is a plan view illustrating a positive electrode shown in FIG. 3;

FIG. 6 is a sectional view illustrating restraints for restraining thebattery body;

FIG. 7 is a plan view illustrating first contact sections shown in FIG.6;

FIG. 8 is a plan view illustrating a negative electrode collector towhich a restraining force is applied by the first contact sections;

FIG. 9 is an enlarged view illustrating slits shown in FIG. 7;

FIG. 10 is a plan view illustrating the first modification of anembodiment of the present invention;

FIG. 11 is a plan view illustrating the second modification of anembodiment of the present invention;

FIG. 12 is a sectional view illustrating the third modification of anembodiment of the present invention;

FIG. 13 is a sectional view illustrating the fourth modification of anembodiment of the present invention;

FIG. 14 is a sectional view illustrating the fifth modification of anembodiment of the present invention;

FIG. 15 is a plan view illustrating the fifth modification of anembodiment of the present invention;

FIG. 16 is a sectional view illustrating the sixth modification of anembodiment of the present invention;

FIG. 17 is a sectional view illustrating the battery body and the powergeneration elements shown in FIG. 16;

FIG. 18 is a sectional view illustrating the restraints for restrainingthe battery body.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Embodiments of the present invention are described below with referenceto the accompanying drawings. Ratios of dimensions in the drawings aresometimes exaggerated for convenience of description, and may vary fromactual ratios.

FIG. 1 is an oblique view illustrating a secondary battery according toan embodiment of the present invention, and FIG. 2 is a sectional viewof the secondary battery shown in FIG. 1.

A secondary battery 10 according to an embodiment of the presentinvention is a non-bipolar lithium-ion secondary battery, and has anegative electrode tab 12, a positive electrode tab 14, and an exteriorbody 16, as indicated in FIG. 1. The secondary battery 10 is configuredas a battery assembly and used as a power source device for a vehicle,for example. The vehicle is an electric automobile or a hybrid electricautomobile, for example.

The negative electrode tab 12 and the positive electrode tab 14 areelectrode terminals comprising highly electroconductive members. Thetabs extend out from inside the exterior body 16, and are used forsending out electric current. The negative electrode tab 12 and thepositive electrode tab 14 are preferably covered by, for example, aheat-resistant and insulating heat-shrinkable tubing, and are therebyreliably prevented from coming in electrical contact with peripheralequipment, wiring, etc.

As indicated in FIG. 2, a battery body 20 and restraints 80 (notillustrated) are disposed inside the exterior body 16, and the exteriorbody 16 is used to prevent shock of external origin or environmentaldegradation. The exterior body 16 is formed by joining all or a portionof an external peripheral part of a sheet member. Examples of thejoining method include thermal fusion bonding.

The battery body 20 has a plurality of power generation elements (unitbatteries) 22. The power generation elements 22 are stacked andelectrically connected in parallel. The restraints 80 (not illustrated)are used for restraining the battery body 20 in a stacking direction Sof the power generation elements 22, as described hereinafter.

The highly electroconductive members constituting the negative electrodetab 12 and the positive electrode tab 14 are aluminum, copper, titanium,nickel, stainless steel, or an alloy thereof, for example.

The sheet member constituting the exterior body 16 is preferablyconstituted from a polymer-metal composite laminate film, for the sakeof weight reduction and thermal conductivity. The polymer ispolypropylene, polyethylene, or another thermoplastic resin material,for example. The metal is, for example, aluminum, stainless steel,nickel, copper, etc. (including alloys of these). The exterior body 16is not limited to being constituted from a pair of laminate films (sheetmembers); for example, a laminate film formed in a bag shape in advancecan be used as well.

The battery body and the power generation elements will next bedescribed in detail.

FIG. 3 is a sectional view illustrating the battery body and the powergeneration elements shown in FIG. 2.

As indicated in FIG. 3, the battery body 20 has negative electrodes 30,separators 50, and positive electrodes 60.

The negative electrodes 30 have a negative electrode collector 32 andsubstantially rectangular negative electrode active material layers 34.The negative electrode active material layers 34 are disposed on bothsurfaces of the negative electrode collector 32 in the stackingdirection S. In other words, the negative electrode collector 32 isshared by adjacent negative electrodes 30. The negative electrodecollector 32 is constituted from a copper foil having a thickness of,e.g., about 1-100 μm.

The negative electrode active material layers 34 contain a negativeelectrode active material and additives, and have a thickness of, e.g.,about 1-100 μm. The negative electrode active material has a compositionwhereby lithium ions can be desorbed during discharging and lithium ionscan be occluded during charging. The additives are a binder and anelectroconductivity auxiliary. The binder is added for a purpose ofmaintaining the structure of the negative electrode, and has a functionfor binding together constituent materials of the negative electrodeactive material layers 34, and a function for causing the negativeelectrode active material layers 34 to bind to the negative electrodecollector 32. The binder is constituted from carboxymethylcellulose(CMC) and styrene-butadiene rubber (SBR), for example. Theelectroconductivity auxiliary is constituted from a carbon material,etc., having good electrical conductivity, and is blended in order toenhance the electroconductivity of the negative electrode activematerial layers 34. The carbon material is acetylene black, for example.

In the present embodiment, the negative electrode active materialincludes a silicon-based material. Silicon has a better lithium ionoccluding ability per unit volume than graphite, etc., which makes itpossible to increase the capacity of a secondary battery. In particular,in the present embodiment, splitting of the negative electrode collector32 caused by expansion and contraction of the negative electrode activematerial layer 34 is suppressed, as described hereinafter, and anegative electrode active material containing silicon, which has highexpansibility, can therefore easily be applied.

The positive electrodes 60 have a positive electrode collector 62 and asubstantially rectangular positive electrode active material layer 64. Apositive electrode active material layer 64 is disposed on both surfacesof the positive electrode collector 62 in the stacking direction S. Inother words, the positive electrode collector 62 is shared by adjacentpositive electrodes 60.

The positive electrode collector 62 has a thickness of about 1-100 μm,for example. The material constituting the positive electrode collector62 is the same as the material constituting the negative electrodecollector 32.

The positive electrode active material layers 64 contain a positiveelectrode active material and additives, and have a thickness of about1-100 μm, for example. The positive electrode active material has acomposition whereby lithium ions can be desorbed during charging andlithium ions can be occluded during discharging. The positive electrodeactive material is LiNiCoAlO₂, for example. The additives are a binderand an electroconductivity auxiliary. The binder is added for a purposeof maintaining the structure of the positive electrode, and has afunction for binding together constituent materials of the positiveelectrode active material layers 64, and a function for causing thepositive electrode active material layers 64 to bind to the positiveelectrode collector 62. The binder is constituted from polyvinylidenefluoride (PVdF), for example. The electroconductivity auxiliary isblended in order to enhance the electroconductivity of the positiveelectrode active material layers 64, and is the same as theelectroconductivity auxiliary in the negative electrodes 30.

The separators 50 are substantially rectangular porous material sheets(porous film) formed from polypropylene, and have a thickness of about1-50 μm, for example. The separators 50 are disposed between thenegative electrode active material layers 34 and the positive electrodeactive material layers 64, and the negative electrode active materiallayers 34 and the positive electrode active material layers 64 face eachother, interposed by the separators 50.

The separators 50 are impregnated with an electrolyte, and constituteelectrolyte layers for retaining the electrolyte. The electrolyte is aliquid electrolyte, for example. In other words, the separators 50 havea function for ensuring conductivity of lithium ions (carrier ions)between the positive electrodes 60 and the negative electrodes 30, andfunction as barriers between the positive electrodes 60 and the negativeelectrodes 30.

Each of the power generation elements 22 is constituted from a negativeelectrode collector 32, a negative electrode active material layer 34, aseparator 50, a positive electrode active material layer 64, and apositive electrode collector 62.

The negative electrode active material layer 34 is configured so as tohave a larger area than the positive electrode active material layer 64.A decrease in a facing area between the negative electrode activematerial layer 34 and the positive electrode active material layer 64 isthereby suppressed even when the positive electrode active materiallayer 64 becomes misaligned with the negative electrode active materiallayer 34. Fluctuation in power generation capacity due to a decrease inthe facing area is therefore prevented.

The negative electrode collectors, the positive electrode collector, thesilicon-based material of the negative electrode active material, thenegative electrode binder, the positive electrode active material, thepositive electrode binder, the electroconductivity auxiliary, theseparators, and the composition of the electrolyte, etc., will next bedescribed in this order.

The material constituting the negative electrode collectors and thepositive electrode collectors is not limited to copper; another metal oran electroconductive resin is applicable. The other metal is aluminum,nickel, iron, stainless steel, titanium, a cladding material of nickeland aluminum, a cladding material of copper aluminum, or a claddingmaterial of a combination of these metals, for example. Theelectroconductive resin is an electroconductive polymer material, anelectroconductive polymer material to which an electroconductive filleris added, or a non-electroconductive polymer material to which anelectroconductive filler is added, for example.

The silicon-based material of the negative electrode active material issilicon metal (elemental Si), a silicon alloy, a silicon oxide, asilicon compound, or a silicon semiconductor, for example. The siliconalloy includes aluminum, tin, zinc, nickel, copper, titanium, vanadium,magnesium, lithium, or another metal alloyed with silicon. The siliconalloy is preferably a Si—Sn—Ti-based alloy or another alloy based onthree or more elements. The silicon oxide is SiO₂, SiO, SiO_(x), etc.The SiO_(x) is a mixture of amorphous SiO₂ particles and Si particles(where x represents a number of oxygen atoms satisfying a valence ofSi). The silicon compound contains at least one component selected fromthe group consisting of lithium, carbon, aluminum, tin, zinc, nickel,copper, titanium, vanadium, and magnesium, for example. The negativeelectrode active material is not limited to a form including only onetype of silicon-based material.

The negative electrode binder is not limited to a form includingstyrene-butadiene rubber (SBR) and carboxymethylcellulose (CMC). Forexample, a rubber-based binder other than styrene-butadiene rubber (SBR)or a water-soluble polymer other than carboxymethylcellulose (CMC) isalso applicable as the negative electrode binder. The negative electrodebinder may be a single material, or three or more materials may be usedjointly as needed.

The positive electrode active material is not limited to a formincluding LiNiCoAlO₂, and LiMn₂O₄, LiNiO₂, LiCoO₂, LiNiMnCoO₂, LiFePO₄,etc., for example, are also applicable as appropriate.

The positive electrode binder is not limited to being constituted frompolyvinylidene fluoride (PVdF).

The electroconductivity auxiliary is not limited to being constitutedfrom acetylene black. For example, a carbon powder other than acetyleneblack, vapor-grown carbon fibers (VGCF®) and other carbon fibers,expanded graphite, etc. are also applicable.

The porous material sheet constituting the separators is not limited tobeing formed from polypropylene. For example, the porous material sheetcan also be formed from polyethylene or another polyolefin other thanpolypropylene, a layered body in which a plurality of polyolefins arelayered, polyimides, aramids, polyvinylidenefluoride-hexafluoropropylene (PVdF-HFP), glass fibers, etc. Theseparators can also be constituted from nonwoven fabric sheets. Thenonwoven fabric sheets are formed from cotton, rayon, acetate, Nylon®,polyester, a polyolefin such as polyethylene or polypropylene,polyimides, aramids, etc., for example.

The liquid electrolyte retained by the separators has a solvent and alithium salt as a supporting electrolyte dissolved in the solvent.Examples of the lithium salt is Li(CF₃SO₂)₂N, Li(C₂F₅SO₂)₂N, LiPF₆,LiBF₄, LiAsF₆, LiTaF₆, LiClO₄, or LiCF₃SO₃. The solvent is ethylenecarbonate (EC), propylene carbonate (PC), butylene carbonate (BC),vinylene carbonate (VC), dimethyl carbonate (DMC), diethyl carbonate(DEC), ethyl methyl carbonate (EMC), or methyl propyl carbonate (MPC),for example.

The electrolyte retained by the separators is not limited to a liquidelectrolyte. For example, the separators can also retain a gel polymerelectrolyte. The gel polymer electrolyte is constituted from a matrixpolymer (host polymer) infused with a liquid electrolyte. The matrixpolymer is an ion-conductive polymer. Examples of the ion-conductivepolymer include polyethylene oxide (PEO), polypropylene oxide (PPO), andcopolymers thereof.

A structure of the negative electrodes and the positive electrodes willnext be described.

FIGS. 4 and 5 are plan views illustrating a negative electrode and apositive electrode shown in FIG. 3.

As indicated in FIG. 4, the negative electrode collector 32 of thenegative electrode 30 has an active material region 40 and anon-active-material region 46. The active material region 40 is a regionin which the negative electrode active material layer 34 is disposed ona surface, and has a facing section 42 and a non-facing section 44.

The facing section 42 is a region facing the positive electrode activematerial layer 64, interposed by the separator 50, and the non-facingsection 44 is a region not facing the positive electrode active materiallayer 64, the non-facing section 44 being positioned on a periphery (soas to surround the facing section 42) of the facing section 42 (see FIG.3).

The non-active-material region 46 protrudes from one side 41 of thesubstantially rectangular active material region 40, and is joined(fixed) to the negative electrode tab 12 for drawing electric currenttoward the outside.

As indicated in FIG. 5, the positive electrode collector 62 of thepositive electrode 60 has an active material region 70 and anon-active-material region 76. The active material region 70 is a regionin which the positive electrode active material layer 64 is disposed ona surface, and is a facing section 72 facing the negative electrodeactive material layer 34, interposed by the separator 50.

The non-active-material region 76 protrudes from one side 71 of thesubstantially rectangular active material region 70, and is joined(fixed) to the positive electrode tab 14 for drawing electric currenttoward the outside.

The non-active-material region 76 is positioned so as not to overlap thenon-active-material region 46 of the negative electrode collector 32 inthe stacking direction S. Ultrasonic welding or resistance welding, forexample, is applied to join the negative electrode tab 12 and thenon-active-material region 46 of the negative electrode 30 and to jointhe positive electrode tab 14 and the non-active-material region 76 ofthe positive electrode 60.

The restraints will next be described.

FIG. 6 is a sectional view illustrating the restraints for restrainingthe battery body.

As indicated in FIG. 6, the restraints 80 are substantially U-shaped incross section, and have a first contact section 81, a second contactsection 88, and a connecting section 89, and are used for restrainingthe battery body 20 in the stacking direction S. In the presentembodiment, the secondary battery 10 has four restraints 80 disposedalong a periphery of the battery body 20. The number of restraints 80and the positions in which the restraints 80 are disposed are notlimited to the above configuration.

The first contact sections 81 and the second contact sections 88 areused to apply a restraining force to one and another outermost layer ofthe battery body 20 in the stacking direction S. The restraining forceis based on an adhesion force generated by adhesive material layers 92.

In the present embodiment, negative electrode collectors 32 arepositioned in one and the other outermost layer of the battery body 20.Consequently, the first contact sections 81 and the second contactsections 88 apply restraining force to the negative electrode collectors32 positioned in one and the other outermost layer of the battery body20. The one and the other outermost layers of the battery body 20 mayalso be negative electrode active material layers 34 disposed on asurface of a negative electrode collector 32, but the example describedbelow is of a case in which one and the other outermost layer of thebattery body 20 are negative electrode collectors 32.

The connecting sections 89 extend alongside the battery body 20 in thestacking direction S and connect the first contact sections 81 and thesecond contact sections 88.

The restraints 80 are formed from a pressure-sensitive-adhesive filmhaving a base material layer 90 and an adhesive material layer 92supported by the base material layer 90. The pressure-sensitive-adhesivefilm is Kapton® tape, for example. The base material layer 90 isconstituted from a polyimide film, etc. The adhesive material layer 92is constituted from a silicon-based adhesive material, an acrylic-basedadhesive material, etc. The pressure-sensitive-adhesive filmconstituting the connecting section 89 does not have the adhesivematerial layer 92, but can also be constituted so as to have theadhesive material layer 92, as needed.

The first contact sections 81 will next be described in detail. Thesecond contact sections 88 have the same structure as the first contactsections 81 and will therefore not be described below, in order to avoidredundant description.

FIG. 7 is a plan view illustrating the first contact sections shown inFIG. 6, FIG. 8 is a plan view illustrating a negative electrodecollector to which restraining force is applied by the first contactsections, and FIG. 9 is an enlarged view illustrating slits shown inFIG. 7.

The first contact sections 81 shown in FIG. 7 are configured so that astress occurring at boundaries B₁ of contact regions 33A and anon-contact region 33B shown in FIG. 8 is less than a breaking strengthof the negative electrode collector 32. The contact regions 33A areregions in which the first contact sections 81 are in contact with asurface of the outermost layer (negative electrode collector 32 in thepresent example) of the battery body 20. The non-contact region 33B is aregion in which the first contact sections 81 are not in contact. Thestress is based on the restraining force of the first contact sections81 and expansion and contraction of the negative electrode 30 due to achange in volume of the negative electrode active material layers causedby charging and discharging.

Specifically, as indicated in FIG. 9, the first contact sections 81 aresubstantially rectangular, and each have an end face 82, a base section83, side faces 84, 85, and slits 86.

The base section 83 is linked to the connecting section 89 extendingalongside the battery body 20. The end face 82 is a distal end locatedon an opposite side from the base section 83 and is positioned so as toface the facing section 42. The side faces 84, 85 link the end face 82and the base section 83.

The slits 86 extend toward the base section 83 from the end face 82, andreach at least to a position facing a boundary B₂ of the facing section42 and the non-facing section 44. The slits 86 expand and contract alongthe end face 82 (in an extension direction of the end face 82), and thestress occurring at the boundaries (periphery of the contact regions33A) B₁ is thereby dispersed (relieved).

In other words, the first contact sections 81 are configured so as toexpand and contract in accordance with the expansion and contraction ofthe negative electrode 30, and the stress occurring at the boundaries(periphery of the contact regions 33A) B₁ is thereby made less than thebreaking strength of the negative electrode collector 32.

Consequently, it is possible to suppress splitting of the negativeelectrode collector 32 at the boundaries (periphery of the contactregions 33A) B₁, caused by expansion and contraction of thesilicon-containing negative electrode active material layer. As aresult, a decrease in battery output and/or battery capacity based onlocalized splitting of the negative electrode collector 32 issuppressed, growth of localized splitting of the negative electrodecollector 32 due to repeated charging and discharging of the secondarybattery is avoided, and deterioration of cycle characteristics (servicelife) is suppressed.

A method of forming the slits 86 is not particularly limited, and acutter can be used, for example.

First to sixth modifications will next be described in order.

FIG. 10 is a plan view illustrating the first modification of anembodiment of the present invention.

The restraints 80 can also have a first contact section 81A shown inFIG. 10. In addition to the slits 86 extending toward the base section83 from the end faces 82, the first contact section 81A furthermore hasslits 87A extending toward the side face 85 from the side face 84, andslits 87B extending toward the side face 84 from the side face 85. Theslits 87A, 87B expand and contract along the side faces 84, 85 (in anextension direction of the side faces 84, 85), and the stress occurringat the boundaries (periphery of the contact regions 33A) B₁ is therebydispersed (relieved).

FIG. 11 is a plan view illustrating the second modification of anembodiment of the present invention.

The restraints 80 can also have a first contact section 81B shown inFIG. 11. The first contact section 81B does not have the slits 86extending toward the base section 83 from the end face 82, and has slits87A extending toward the side face 85 from the side face 84, and slits87B extending toward the side face 84 from the side face 85.

FIG. 12 is a sectional view illustrating the third modification of anembodiment of the present invention.

The secondary battery 10 can also have a restraint 80C shown in FIG. 12.The restraint 80C is constituted from an adhesive material havingelasticity which enables the adhesive material to follow expansion andcontraction of the negative electrode 30, and a first contact section81C, a second contact section 88C, and a connecting section 89C areintegrated in the restraint 80C. A restraining force of the firstcontact section 81C is based on an adhesive force generated by theadhesive material. The adhesive material is styrene-butadiene rubber(SBR), polyvinylidene fluoride (PVdF), a polyimide, polyacrylic acid, oranother adhesive rubber material.

In this case, stress occurring at the boundaries (periphery of thecontact regions 33A) B₁ is dispersed (relieved) by expansion andcontraction of the first contact sections 81C as such. Specifically, anelasticity (Young's modulus) of the adhesive material is adjusted inadvance so that the stress occurring at the boundaries B₁ by expansionand contraction of the negative electrode 30 in an actual usageenvironment of the secondary battery 10 is less than the breakingstrength of the negative electrode collector 32. The restraint 80C canbe formed by applying a liquid adhesive material to a predeterminedregion and then drying the adhesive material.

FIG. 13 is a sectional view illustrating the fourth modification of anembodiment of the present invention.

The secondary battery 10 can also have a restraint 80D shown in FIG. 13.The restraint 80D is formed from a pressure-sensitive-adhesive filmhaving a base material layer 90D and an adhesive material layer 92Dsupported by the base material layer 90D, and a first contact section81D, a second contact section 88D, and a connecting section 89D areintegrated in the restraint 80D. A restraining force of the firstcontact section 81D is based on an adhesive force generated by theadhesive material layer 92D.

The adhesive material layer 92D is constituted from an adhesive materialhaving elasticity which enables the adhesive material to followexpansion and contraction of the negative electrode 30, the same as inthe third modification. In other words, the first contact section 81Dcorresponds to a configuration in which the base material layer 90D iscombined with the first contact section 81C, and stress occurring at theboundaries (periphery of the contact regions 33A) B₁ is dispersed(relieved) by expansion and contraction of the adhesive material layer92D as such.

FIG. 14 and FIG. 15 are a sectional view and a plan view, respectively,illustrating the fifth modification of an embodiment of the presentinvention.

The secondary battery 10 can also have a restraint 80E shown in FIG. 14.The restraint 80E is formed from a pressure-sensitive-adhesive filmhaving a base material layer 90 and adhesive material layers 92E, and afirst contact section 81E, a second contact section 88E, and aconnecting section 89 are integrated in the restraint 80E. As indicatedin FIG. 15, the adhesive material layers 92E are constituted fromadhesive materials 93 disposed intermittently on the base material layer90. A restraining force of the first contact section 81E is based on anadhesive force generated by the adhesive materials 93 (adhesive materiallayers 92E).

The adhesive force generated by the adhesive material layers 92E is setso as to be less than the breaking strength of the negative electrodecollector 32 by adjusting a configuration in which the adhesivematerials 93 are arranged. Consequently, the first contact section 81Edisperses (relieves) stress occurring at the boundaries (periphery ofthe contact regions 33A) B₁. In other words, the stress can be made lessthan the breaking strength of the negative electrode collector 32. Theconfiguration whereby the adhesive force generated by the adhesivematerial layers 92E is set is not particularly limited to the aboveconfiguration.

FIG. 16 is a sectional view illustrating the sixth modification of anembodiment of the present invention, FIG. 17 is a sectional viewillustrating the battery body and the power generation elements shown inFIG. 16, and FIG. 18 is a sectional view illustrating the restraints forrestraining the battery body.

The restraints 80 can also be applied to a secondary battery 10F and abattery body 20F shown in FIG. 16. In order to avoid redundantdescription, members having the same function as members of thesecondary battery 10 will not be described below.

Specifically, the secondary battery 10F is a bipolar lithium-ionsecondary battery, and has a negative electrode tab 12F, a positiveelectrode tab 14F, and an exterior body 16. A battery body 20F,restraints 80 (see FIG. 18), and a seal (not illustrated) are disposedin the exterior body 16. The negative electrode tab 12F and the positiveelectrode tab 14F are disposed outside the battery body 20F, and areconfigured so as to at least cover an entire electrode projectionsurface.

As indicated in FIG. 17, the battery body 20F has negative electrodeactive material layers 34, separators 50, positive electrode activematerial layers 64, and collectors 96. The negative electrode activematerial layers 34 include a silicon-based material, and are disposed onone surface of the collectors 96. The positive electrode active materiallayers 64 are disposed on another surface of the collectors 96. Anegative electrode active material layer 34 and a collectors 96constitute a negative electrode 30F, and a positive electrode activematerial layer 64 and a collector 96 constitute a positive electrode60F. In other words, the collector 96 is a bipolar collectors shared bythe negative electrode 30F and the positive electrode 60F (serving as anegative electrode collector and a positive electrode collector).

The separators 50 are disposed between the negative electrode activematerial layers 34 and the positive electrode active material layers 64.Consequently, a collector 96, a negative electrode active material layer34, a separator 50, a positive electrode active material layer 64, and acollector 96 constitute a power generation element (single unit battery)22F. Power generation elements 22F are stacked and electricallyconnected in series.

The negative electrode active material layers 34 are configured so as tohave a larger area than the positive electrode active material layers64. Consequently, an active material region 40 of the collectors 96 inwhich the negative electrode active material layers 34 are disposed hasa facing section 42 in which the electrode active material layers 64 arefaced, interposed by the separators 50, and a non-facing section 44 inwhich the positive electrode active material layers 64 are not faced,the non-facing section 44 being positioned on the periphery (so as tosurround the facing section 42) of the facing section 42 (see FIG. 17).

The seal is disposed so as to surround a periphery of the positiveelectrode active material layers 64 and the negative electrode activematerial layers 34, and is provided to seal at least a portion of anouter circumferential section of the power generation elements 22. Theseal can also be omitted, as appropriate, in accordance with aconfiguration of the electrolyte (electrolytic solution).

As indicated in FIG. 18, the restraints 80 are substantially U-shaped incross section, and have a first contact section 81, a second contactsection 88, and a connecting section 89, and are used for restrainingthe battery body 20F in the stacking direction S. The first contactsections 81 and the second contact sections 88 apply a restraining forceto the collectors 96 positioned on one and another outermost layer ofthe battery body 20F.

In the sixth modification, a collector 96 for functioning as a negativeelectrode collector and a collector 96 for functioning as a positiveelectrode collector are positioned in one and the other outermost layerof the battery body 20F. Consequently, the first contact sections 81 arein contact with a collector 96 for functioning as a negative electrodecollector.

The first contact sections 81 are therefore configured so that a stressoccurring at boundaries B₁ (see FIG. 8) of contact regions 33A and anon-contact region 33B is less than a breaking strength of thecollectors 96. In other words, the stress occurring at the boundaries(periphery of the contact regions 33A) B₁ is made less than the breakingstrength of the collectors 96. Consequently, it is possible to suppresssplitting of the collectors 96 at the boundaries (periphery of thecontact regions 33A) B₁, caused by expansion and contraction of thesilicon-containing negative electrode active material layers.

In FIG. 16, the collector 96 positioned in an uppermost layer does nothave a positive electrode active material layer 64, and the collector 96positioned in a lowermost layer does not have a negative electrodeactive material layer 34. The reason for this is that a positiveelectrode active material layer 64 and a negative electrode activematerial layer 34 positioned on outsides of collectors 96 positioned inthe uppermost layer and the lowermost layer do not participate in abattery reaction. However, as needed, the battery can also be configuredso as to have a bipolar electrode structure.

In the secondary battery according to the present embodiment describedabove in which a negative electrode active material layer containingsilicon is applied, a configuration is adopted whereby stress occurringat the boundaries of the non-contact region and the contact regions ofthe first contact sections is less than the breaking strength of thenegative electrode collectors, and the stress is relieved. Splitting ofthe negative electrode collectors at the boundaries (periphery of thecontact regions) of the contact regions and the non-contact region istherefore suppressed. In other words, a secondary battery can beprovided in which it is possible to suppress splitting of the negativeelectrode collectors caused by contraction and expansion of thesilicon-containing negative electrode active material layers.

When the first contact sections are configured so as to expand andcontract in accordance with contraction and expansion of the negativeelectrodes, stress occurring at the boundaries of the non-contact regionand the contact regions of the first contact sections can be relieved bythe expansion and contraction of the first contact sections. In otherwords, the stress can be made less than the breaking strength of thenegative electrode collectors.

When slits are provided which extend toward the base section from theend face and reach at least to a position facing the boundary of thefacing section and the non-facing section, stress occurring at theboundaries of the non-contact region and the contact regions of thefirst contact sections, positioned at end faces of the first contactsections, can be dispersed (relieved) by expansion and contraction ofthe slits along the end faces (in the extension direction of the endfaces) of the first contact sections.

When slits are provided which extend from a side face toward anotherside face, stress occurring at the boundaries of the non-contact regionand the contact regions of the first contact sections, positioned at endfaces of the first contact sections, can be dispersed (relieved) byexpansion and contraction of the slits along the side faces (in theextension direction of the side faces) of the first contact sections.

When the first contact sections are formed from an adhesive materialhaving elasticity which enables the adhesive material to followexpansion and contraction of the negative electrodes, stress occurringat the boundaries of the non-contact region and the contact regions ofthe first contact sections, positioned at end faces of the first contactsections, can be dispersed (relieved) by expansion and contraction ofthe first contact sections as such. When the restraints are formedentirely from the adhesive material, the structure of the restraints canbe simplified.

When the first contact sections have an adhesive material layer formedfrom an adhesive material having elasticity which enables the adhesivematerial to follow expansion and contraction of the negative electrodes,and a base material layer for supporting the adhesive material layer,the adhesive material (adhesive material layer) is easily handled.

When the first contact sections have an adhesive material layer and abase material layer for supporting the adhesive material layer, and theadhesive force generated by the adhesive material layer is set so as tobe less than the breaking strength of the negative electrode collectors,stress occurring at the boundaries of the non-contact region and thecontact regions of the first contact sections can be relieved and madeless than the breaking strength of the negative electrode collectors.When the adhesive material constituting the adhesive material layer isdisposed intermittently on the base material layer, the adhesive forcegenerated by the adhesive material layer can easily be set.

When the restraints are formed from a pressure-sensitive-adhesive film,the structure of the restraints can be simplified.

When the area of the negative electrode active material layers isgreater than the area of the positive electrode active material layers,an effect of misalignment on the facing area can be suppressed, andfluctuation in power generation capacity can be prevented.

The present invention is not limited to the embodiment described above,and various modifications thereof are possible within the scope of theclaims. For example, the secondary battery can also be used in the formof a serialized and/or parallelized assembled battery. The method forconfiguring the first contact sections so as to expand and contract inaccordance with expansion and contraction of the negative electrodes isnot limited to providing slits or using an adhesive material havingelasticity which enables the adhesive material to follow expansion andcontraction of the negative electrodes. Furthermore, the first to fifthmodifications can also be applied and used in the sixth modification.

The invention claimed is:
 1. A secondary battery comprising: a batterybody having a plurality of stacked power generation elements; and arestraint restraining the battery body in a stacking direction of thepower generation elements; the power generation elements having apositive electrode having a positive electrode collector in which apositive electrode active material layer is disposed, an electrolytelayer containing an electrolyte, and a negative electrode having anegative electrode collector which includes a negative electrode activematerial layer containing silicon; the positive electrode activematerial layer and the negative electrode active material layer facingeach other, and being interposed by the electrolyte layer; the restrainthaving a first contact section and a second contact section thatrespectively contact a surface of one outermost layer and anotheroutermost layer of the battery body in the stacking direction and thatapply a restraining force; the negative electrode being positioned inthe one outermost layer, and a surface of the negative electrode havinga contact region in contact with the first contact section and anon-contact region which is not in contact with the first contactsection, the surface of the negative electrode having the contact regionand the non-contact region being the same surface; the first contactsection being configured so that a stress occurring at a boundary of thecontact region and the non-contact region is less than a breakingstrength of the negative electrode collector; the stress being based onthe restraining force of the first contact section, and expansion andcontraction of the negative electrode due to a change in volume of thenegative electrode active material layer caused by charging anddischarging; the restraint having a connecting section that connects thefirst contact section and the second contact section; the connectingsection extending alongside the battery body in the stacking direction;the negative electrode active material layer having a facing sectionfacing the positive electrode active material layer, interposed by theelectrolyte layer, and a non-facing section positioned on a periphery ofthe facing section and not facing the positive electrode active materiallayer; the first contact section being substantially rectangular and hasa base section linked to the connecting section, an end face positionedon an opposite side from the base section, side faces for linking theend face and the base section, and a first slit; and the first slitextending toward the base section from the end face and reaches at leastto a position facing a boundary of the facing section and the non-facingsection.
 2. The secondary battery according to claim 1, wherein thefirst contact section is configured so as to expand and contract inaccordance with expansion and contraction of the negative electrode. 3.The secondary battery according to claim 1, wherein the first contactsection further comprises a second slit extending from one of the sidefaces toward another of the side faces.
 4. The secondary batteryaccording to claim 1, wherein the restraint is formed from apressure-sensitive-adhesive film having an adhesive material layer and abase material layer that supports the adhesive material layer; and therestraining force of the first contact section is based on an adhesiveforce generated by the adhesive material layer.
 5. The secondary batteryaccording to claim 1, wherein the restraint is formed from apressure-sensitive-adhesive film.
 6. The secondary battery according toclaim 1, wherein the negative electrode active material layer has anarea that is greater than an area of the positive electrode activematerial layer.